Covalent Organic Frameworks for Efficient Energy Electrocatalysis: Rational Design and Progress

Abstract

An efficient catalyst with a precisely designed and predictable structure is highly desired to optimize its performance and understand the mechanism beyond the catalytic activity. Covalent organic frameworks (COFs), as an emerging class of framework materials linked by strong covalent bonds, simultaneously allow precise structure design with predictable synthesis and show advantages of large surface areas, tunable pore sizes, and unique molecular architectures. Although the research on COF‐based electrocatalysts is at an early age, significant progress has been made. Herein, the recent significant progress in the design and synthesis of COFs as highly efficient electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is summarized. Design principles for COFs as efficient electrocatalysts are discussed by considering essential factors for catalyzing the OER, ORR, and HER processes at the molecular level. Herein, a summary on the in‐depth understanding of the catalytic mechanism and kinetics limitations of COFs provides a general instruction for further exploring their vast potential for designing highly efficient electrocatalysts.

Covalent organic frameworks with Ni-Bis(dithiolene) and Co-porphyrin units as bifunctional catalysts for Li-O 2 batteries

“…Metal-bis(dithiolene) and metalloporphyrin moieties are promising active sites for OER and ORR catalysis ( 30 , 31 ). Metal-bis(dithiolene) units have π-conjugated electronic structures and rich redox activity, which have been widely applied in the design of electrode materials ( 32 ).…”

Anchoring boron on a covalent organic framework as an efficient single atom metal-free photo-electrocatalyst for nitrogen fixation: a first-principles analysis

“…Due to these distinguished properties of COFs, they can act as a potential platform for various applications, such as heterogeneous catalysis, 40 optoelectronic devices, 41 storage, 42 gas separation, 43 batteries, 44 semiconductors, 45 and electronic devices. 46 The porosity of COFs is usually larger than that of other materials, which helps in the diffusion of the reactant and product during the reaction and enhances the product yield with high selectivity. 47 So, to date, we understand that both SACs and COFs are very efficient for heterogeneous catalysis.…”

In situ growth of SeOx films on the surface of Ni–Fe–selenide nanosheets as highly active and stable electrocatalysts for the oxygen evolution reaction

“…1 As a pivotal half reaction in water-splitting, the anodic oxygen evolution reaction (OER) is more complex than that of the cathodic hydrogen evolution reaction (HER) due to the four electron transfer processes with high overpotential, which greatly hinders its large-scale industrial application. [2][3][4][5] Although noble metal-based Ir or RuO 2 catalysts can significantly reduce the overpotential and accelerate the kinetics of OER, however, the high cost impedes their extensive applications. [6][7][8][9][10] Thus, over the past few years, many earth-abundant materials with lower cost have been developed to improve the reaction efficiency of OER, such as the transition metal-based selenides, 11,12 nitrides, [13][14][15] sulfides, 16,17 phosphides 18,19 and oxides, [20][21][22] etc., supported non-metallic carbon compounds electrocatalysts.…”